Modular Adsorbent Devices and Applications

ABSTRACT

An adsorbent device includes adsorbent fibers laid along or wound around a center tube. In a specific example, the adsorbent fibers are porous solid amine adsorbent fibers. A module for purifying a raw fluid includes one or more adsorbent devices that can be installed in a vessel in series or in parallel. The module can be configured for axial or cross flow operation and can be employed to purify a gas containing a contaminant such as an acid gas. In some implementations, the module is provided with one or more heating elements that can be used to release adsorbed contaminant to regenerate the adsorbent fibers.

RELATED APPLICATIONS

This application claims the benefit under 35 USC 119(e) of: U.S.Provisional Application No. 63/220,739, filed on Jul. 12, 2021, U.S.Provisional Application No. 63/220,744, filed on Jul. 12, 2021, U.S.Provisional Application No. 63/220,734, filed Jul. 12, 2021, and U.S.Provisional Application No. 63/220,745, filed Jul. 12, 2021, all ofwhich are incorporated herein by this reference in their entirety.

BACKGROUND OF THE INVENTION

Carbon capture, utilization and storage (CCUS) generally refers tovarious technologies believed to play an important role in meetingglobal energy and climate goals. For instance, these technologies areconsidered by many as essential in keeping global temperature increasesbelow 1.5 degrees centigrade (° C.).

CCUS involves capturing CO₂ from diluted gas streams, such as flue gas,air, etc. In the case of flue gas, the CO₂ concentration is in the rangeof 8 to 14 volume %; in the case of ambient atmospheric air, the CO₂concentration is about 450 ppm. Currently, the upfront cost for CO₂capture from a variety of streams is more than 80% of the total CCUScosts. In the case of direct air capture, the upfront cost for CO₂capture is almost 99% of the total CCUS cost.

Conventional adsorbents usually come in beads or pellets, typically from1 to 6 mm in diameter. Adsorbent beds that are packed with beads orpellets typically suffer from low bed packing, high pressure drop, andattrition. Structured sorbents like monoliths and fibers offerimprovement over traditional bead or pellet packed bed structure, asdiscussed, for example, in Critical comparison of structured contactorsor adsorption based gas separation, by S. J. A. DeWitt, A. Sinha, J.Kalyanaraman, F. Zhang, M. J. Realff, and R. P. Lively, Annu. Rev. Chem.Biomol. Eng., 2018, 9, page 129.

The review articles entitled Structured adsorbents in gas separationprocesses by F. Rezaei and P. Webley, Sep. Purif. Techn., 2010, 70, page243 and Structuring adsorbents and catalysts by processing of porouspowders by F. Akhtar, L. Andersson, S. Ogunwumi, N. Hedin, and L.Bergstrom, J. Eur. Ceram. Soc., 2014, 34, page 1643 summarize researchefforts towards structured adsorbents. These references, however, do notoffer any guidance regarding the construction of adsorbent device.

Current available adsorbent reactor configurations, such as fixed beds,moving beds, and fluidized beds, are summarized by C. Dhoke, A. Zaabout,S. Cloete, and S. Amin in the paper Review on reactor configurations foradsorption-based CO ₂ capture, Ind. Eng. Chem. Res., 2021, 60, page3779.

U.S. Pat. Nos. 8,133,308, 8,257,474 and 8,377,172 disclose hollow fiberadsorbents formed from a dope containing a water insoluble polymer and aparticular inorganic adsorbent. However, no information is offeredregarding how the fibers might be packed and utilized for practicalapplications.

U.S. Pat. No. 9,446,349 discloses an adsorption and desorption devicethat encloses hollow fiber membrane adsorbents in a closed containerequipped with a fluid inlet and a fluid outlet. Although the discloseddevice can be utilized as a standalone device, it is unclear how thedevice can be scaled up and stacked for large scale industrialapplications. This is also the case with US Patent Application No.20120247330 and U.S. Pat. No. 8,911,536 which disclose an adsorption anddesorption device formed by enclosing hollow fiber membrane adsorbentsalong with spacers in a closed container equipped with a fluid inlet anda fluid outlet.

An adsorption and desorption device formed by random or wound packing ofadsorbent fibers is described in U.S. Pat. Nos. 9,713,787 and10,464,009. These documents, however, do not provide information on howthe packed device can be utilized in industrial applications.

Adsorbent loaded fibers are described in U.S. Pat. Nos. 10,525,399 and10,525,400. US Patent Application Nos. 20210008523 and 20210031168disclose methods for packing the fibers into a container. Although thedisclosed device can be utilized as a standalone device, the device isdifficult to scale up for large scale industrial applications. U.S. Pat.No. 9,878,291 describes a CO₂ adsorption and regeneration systemutilizing hollow fiber column. However, the hollow fiber columnrepresents a standalone device which cannot be modulized and isdifficult to scale.

U.S. Pat. No. 10,807,034 disclose an adsorbent canister containing sheetadsorbent materials.

SUMMARY OF THE INVENTION

As evidenced by some of the references discussed above, a need continuesto exist for purification methods and adsorbent equipment suitable forthe removal or capture of acid gases. A need also exists for structuredfiber adsorbent devices that can be scaled-up to meet industrialrequirements in a cost-effective manner.

The invention generally relates to approaches for removing an impurity(also referred to herein as a “contaminant”), an acid gas, for instance,from a fluid stream.

In one of its aspects, the invention relates to a device (also referredto herein as an “adsorption device” or “cartridge”) that includesmultiple (a plurality of, i.e., two or more) adsorbent fibers that arelaid parallel to or wound, e.g., helically, around a center tube. Theadsorbent fibers are made from a suitable adsorbent material. In anillustrative example, the adsorbent fibers are porous solid amineadsorbent fibers. The adsorbent fibers can be regenerated by desorbingtrapped impurities using, for instance, heat, reduced pressure or vacuumor a combination thereof.

In a typical approach, the adsorbent fibers are formed in a fiberadsorbent arrangement, also referred to herein as a “fabric”, e.g., in acylindrical shape, around the center tube. Epoxy tubesheets or threadscan be used to seal the ends of the adsorbent fibers. In someembodiments, the fabric is partially wrapped in an impermeable sheet.

The center tube is hollow and provided with holes for fluidcommunication between the adsorbent fibers and the bore (lumen) of thecenter tube. The holes can be disposed along the length, at one of itsends, and so forth.

The device can be configured for longitudinal (axial) flow or cross(transverse) flow.

In another of its aspects, the invention features a process for removinga contaminant from a fluid stream containing the contaminant. In theprocess, a fluid stream is introduced at the shell or exterior side ofthe adsorbent fabric. As the stream passes through the fabric, at leasta portion of the contaminant becomes adsorbed by the adsorbent fibersand a purified fluid stream is collected at the bore side of the centertube. A reversed arrangement (with the raw fluid stream being fed at thebore side of the center tube and a purified fluid stream being withdrawnat the shell side of the fabric) also can be employed.

In some embodiments, the fluid stream containing the contaminant travelsthrough the fiber adsorbent arrangement in an axial direction. Inothers, it traverses the adsorbent fibers arrangement in a cross-flowpattern, e.g., in a direction perpendicular to the length of the centertube.

In a further aspect, the invention relates to a. system, also referredto herein as a “module”, that can include one or more adsorption devicessuch as described above, for example.

Various approaches can be used to construct or use a purification modulecontaining one or more such adsorbent devices. In one embodiment, atleast one adsorbent device is installed in a vessel which can beprovided with an inlet, for introducing a fluid containing a contaminant(also referred to herein as a “raw” fluid) into the vessel, and anoutlet, for collecting a purified (“clean”) fluid. In someimplementations, the module includes multiple (at least two) adsorbentdevices connected in series. In other embodiments, the system includesmultiple adsorbent devices arranged in parallel. The system can includea heating element, for regenerating the adsorbent fibers, for instance.The heating element can be internal or external to the vessel. In anillustrative example, a heat exchanger is installed among severalcartridges installed in a parallel configuration. In another, a vesselthat includes adsorbent cartridges arranged in series is provided with aheating jacket.

During operation, raw fluid is introduced into the vessel and is broughtinto contact with the adsorbent fibers, which trap the contaminant,producing a purified fluid.

Thus, in yet another of its aspects, the invention features a processfor removing a contaminant from a fluid containing the contaminant. Theprocess involves directing the fluid into a module that contains atleast one adsorbent cartridge including adsorbent fibers. The fluidstream is brought into contact with the adsorbent fibers, whereby atleast a portion of the contaminant is adsorbed by the fibers, to producea purified fluid which can be withdrawn (collected) from the module.

In one illustrative approach, the module contains two or morecartridges, arranged in series. In another, the module includescartridges arranged in parallel.

The process can be designed for axial or cross flow pattern. In manycases, the fluid is introduced at the shell or exterior side of theadsorbent fabric and collected from the bore side of the center tube. Areversed flow configuration (with the raw fluid stream being fed at thebore side of the center tube and a purified fluid stream being withdrawnat the shell side of the fabric) also can be employed.

Adsorbent fibers can be regenerated by desorbing trapped impuritiesusing, for instance, heat, reduced pressure, vacuum, or a combinationthereof.

Cartridges, modules and methods described herein can be employed toremove contaminants, e.g., an acid gas such as CO₂, H₂S, SO₂, from fluegases, biogases, hydrogen gas, natural gas, air or other fluid streams.Practicing the invention can be particularly well suited in handling lowconcentration separations, often resulting in high recoveries, lessenergy consumption, better economics, for example in direct air capture,removal of CO₂ for LNG production, and CO₂ capture from flue gases.

The device and/or system can be manufactured in various configurations,presenting many options for addressing specific needs. For instance, themodule design can accommodate systems that rely on a single cartridge aswell as systems in which multiple cartridges are connected in parallelor in series. Available options also include shell side as well as boreside feeding modes. The purification operation can be decoupled fromrecovering the adsorbed contaminant, CO₂, for instance, addingflexibility to the overall process.

Providing an attractive alternative or supplementing membrane separationequipment, devices and/or systems described herein often include robustand rugged adsorbent fibers that can meet any number of processconditions, offering effective stream purification approaches atacceptable cost.

The above and other features of the invention including various detailsof construction and combinations of parts, and other advantages, willnow be more particularly described with reference to the accompanyingdrawings and pointed out in the claims. It will be understood that theparticular method and device embodying the invention are shown by way ofillustration and not as a limitation of the invention. The principlesand features of this invention may be employed in various and numerousembodiments without departing from the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings, reference characters refer to the sameparts throughout the different views. The drawings are not necessarilyto scale; emphasis has instead been placed upon illustrating theprinciples of the invention. Of the drawings:

FIG. 1 is an illustration of a fiber adsorbent cartridge configured foraxial flow, with adsorbent fibers layered around a center tube which hasboth ends equipped with o-rings;

FIG. 2 is an illustration of a fiber adsorbent cartridge configured foraxial flow, with adsorbent fibers layered around a center tube havingone end equipped with a receptacle and the other with an o-ring;

FIG. 3 is an illustration of a fiber adsorbent cartridge configured foraxial flow, with adsorbent fibers layered around a center tube which hasboth ends equipped with o-rings;

FIG. 4 is an illustration of a fiber adsorbent cartridge configured foraxial flow, with adsorbent fibers helically wound around a center tubewhich has both ends equipped with o-rings;

FIG. 5 is an illustration of a fiber adsorbent cartridge configured forcross flow, with adsorbent fibers helically wound around a center tubewhich has both ends equipped with o-rings;

FIG. 6 is a diagram showing an axial fluid flow pattern for an axialflow fiber adsorbent cartridge;

FIG. 7 is a diagram showing a cross flow pattern for a cross flow fiberadsorbent cartridge;

FIG. 8 is an illustration of an adsorbent module in which a singleadsorbent cartridge, configured as shown in FIG. 4 , is installed in avessel;

FIG. 9 is an illustration of a section of a center tube couplingconnecting two adsorbent cartridges;

FIG. 10 is an illustration of a section of a center tube couplingconnecting two adsorbent cartridges and including an optional centeringsupport;

FIG. 11 is an illustration of an adsorbent module including fiveadsorbent cartridges installed in series in a long tubular housing;

FIG. 12 is an illustration of an adsorbent module in which multipleadsorbent cartridges are installed in a parallel configuration;

FIG. 13 is an illustration of an adsorbent module with paralleladsorbent cartridges arranged in rows;

FIG. 14 is an illustration of a module that contains a single adsorbentcartridge and is fitted with an external heating jacket;

FIG. 15 is an illustration of the multi-cartridge module of FIG. 11fitted with an external heating jacket;

FIG. 16 is an illustration of a multi-cartridge adsorbent arrangementwith one internal heat exchanger;

FIG. 17 is an illustration of a multi-cartridge adsorbent arrangementwith two internal heat exchangers;

FIG. 18 is an illustration of an axial flow pattern in a module thatincludes five adsorbent cartridges installed in series, as shown in FIG.11 ;

FIG. 19 is a cross sectional view of an adsorbent module with multiplecartridges installed in a parallel configuration and a heat exchanger;

FIG. 20 is a cross sectional view of another adsorbent module whichincludes multiple cartridges installed in a parallel configuration andmultiple heat exchangers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention now will be described more fully hereinafter withreference to the accompanying drawings, in which illustrativeembodiments of the invention are shown. This invention may, however, beembodied in many different forms and should not be construed as limitedto the embodiments set forth herein; rather, these embodiments areprovided so that this disclosure will be thorough and complete, and willfully convey the scope of the invention to those skilled in the art.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items. Also, all conjunctions usedare to be understood in the most inclusive sense possible. Thus, theword “or” should be understood as having the definition of a logical“or” rather than that of a logical “exclusive or” unless the contextclearly necessitates otherwise. Further, the singular forms and thearticles “a”, “an” and “the” are intended to include the plural forms aswell, unless expressly stated otherwise. It will be further understoodthat the terms: includes, comprises, including and/or comprising, whenused in this specification, specify the presence of stated features,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,integers, steps, operations, elements, components, and/or groupsthereof. Further, it will be understood that when an element, includingcomponent or subsystem, is referred to and/or shown as being connectedor coupled to another element, it can be directly connected or coupledto the other element or intervening elements may be present.

It will be understood that although terms such as “first” and “second”are used herein to describe various elements, these elements should notbe limited by these terms. These terms are only used to distinguish oneelement from another element. Thus, an element discussed below could betermed a second element, and similarly, a second element may be termed afirst element without departing from the teachings of the presentinvention.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

The invention generally relates to fluid purification equipment andtechniques. The adsorption device (cartridge) described hereinincorporates adsorbent fibers. One or more such devices can be assembledin a system (module). Further embodiments of the invention pertain tomethods for preparing and/or using such adsorbent devices and/ormodules.

Adsorbent devices that can be employed to prepare a module, for example,typically include multiple also referred to herein as a “plurality of”(i.e., at least two) adsorbent fibers disposed in various configurations(e.g., laid along to, typically in parallel, or wound around, e.g.,helically) relative to a center tube.

In many cases, the adsorbent fibers form an arrangement also referred toherein as “bundle” or “fabric” around the center tube. The adsorbentfibers can be hollow adsorbent fibers. For many applications, however,non-hollow adsorbent fibers provide more adsorbing material for a givenvolume. In many embodiments, the fabric has a cylindrical shape. Itsthickness may vary, depending on the type of cartridge, volume of gastreated or application. Typically, the fiber adsorbent arrangement has athickness of at least about 1 inch, such as within a range of from about1 inch to about 50 inches, preferably, from about 3 inches to about 20inches.

The center tube can be a cylindrical hollow tube with openings (alsoreferred to as holes, orifices or perforations) that allow fluidcommunication between an exterior (shell) surface of the fabric and thebore or lumen of the center (also referred to as “core”) tube. Thecenter tube can be made from any nonimpermeable material that iscompatible with the fluid streams being processed, e.g., metal, glass,wood, plastic, composite laminate, and the like. In an illustrativeexample, the center tube has a length within a range of from about 12inches to about 100 inches and a diameter within a range of from about0.5 inches to about 3 inches. The placement of the holes typically willdepend on the kind of flow intended for the cartridge, as furtherdescribed below.

Preparing an adsorbent fiber arrangement around the center tube ofteninvolves employing more than one fiber at the time, using, for instance,filaments of 4 to 32 fibers. Methods for laying or winding fibers invarious configurations are known in the art, as described, for instance,in U.S. Pat. Nos. 5,837,033, 3,339,341 and 4,940,617, the contents ofwhich are incorporated herein by this reference. Other approaches, e.g.,those developed or refined in the future, also can be employed.

The fiber packing density can be controlled. With computerized windingtechniques, for instance, the packing density can be preciselycontrolled using different winding parameters, such as winding angle,fiber spacing, phases, etc. This is described in U.S. Pat. No.6,638,479, which is incorporated herein by this reference in itsentirety.

The precision control of the fiber spacing offers the advantage of fastand uniform mass transfer. The pressure drop across a fiber adsorbentcan be given as:

$\begin{matrix}{\frac{\Delta p}{L} = {{\frac{150\mu}{d^{2}}\left( \frac{1 - \varepsilon}{\varepsilon} \right)^{2}\left( \frac{v}{\varepsilon} \right)} + {\frac{1.75\rho}{d}\left( \frac{1 - \varepsilon}{\varepsilon} \right)\left( \frac{v}{\varepsilon} \right)^{2}}}} & (1)\end{matrix}$

where L is the length, d is the cartridge diameter, ε is void fraction,and υ, μ are gas superficial velocity and viscosity, respectively.Equation 1 predicts that the pressure drop is a quadratic function ofthe interstitial velocity of the gas flow, and voidage.

The ends of the adsorbent fibers can be sealed with epoxy tube sheets.Techniques are described, for instance in U.S. Pat. Nos. 6,042,677,6,290,756 and 6,709,494, which are incorporated herein in their entiretyby this reference.

In some cases, e.g., if using computer controlled winding techniques toconstruct the device, threads can be used on one or both ends to holdthe fiber tightly in place, as described, for example, in U.S. Pat. No.6,638,479, which is incorporated herein in its entirety by thisreference. Generally, these threads can provide a very effective sealfor the fiber ends, rendering redundant epoxy sealing. Thus, in manyimplementations, the device uses epoxy sealing, or threads, or acombination of both.

In many embodiments of the invention, the complete device has a cylindershape with the center tube extending outside the fiber arrangement. Theends of the center tube can be both in the same configuration or in areciprocal configuration. In contrast to arrangements that employ hollowfiber membranes, contaminants such as acid gases are trapped or capturedin the adsorbent material, which can be regenerated by cyclingprocesses. Thus, the cartridge described herein does not need to providefor the extraction of a fluid fraction that is enriched withcontaminant, as in the case of membrane separation devices.

The fiber arrangement can be covered (at least in part) with animpermeable wrap, with another type of covering or left uncovered. Thechoice depends, at least in part, on the flow configurationcharacterizing the cartridge.

Shown in FIG. 1 is cartridge 10 including center tube 12, provided withopenings 14, and fiber arrangement (fabric) 16, which includes aplurality of adsorbent fibers 18, laid along, e.g., parallel, to thelength of center tube 12.

Holes 14 are disposed at one end of the center tube and can include asingle or, typically, two or more (e.g., 4, 50, 100, 200, etc.,depending on the center tube diameter and treated gas flow volume)perforations.

In the embodiment of FIG. 1 , fibers 18 are secured by epoxy tubesheets20 and 22.

Wrap 24 partially encases fiber arrangement 16, being provided with wrapopening 26. Wrap 24 is made of an impermeable material, e.g., sheetplastic, metal, fiberglass, and so forth. In specific examples, the wrapmaterial has a high thermal conductivity, such as, for instance,stainless steel sheet, copper sheet, etc. Materials characterized byhigh thermal conductivity can facilitate the heating of the adsorbentsin systems in which a heat exchanger is placed outside of the cartridge.

As seen in FIG. 1 , wrap 24 covers the section of the fiber arrangement16 that is disposed over openings 14, while providing fluidcommunication between the exterior (at the shell side) and the fiberarrangement 16, through opening 26. This arrangement allows fluid toenter or exit the adsorbent fibers and generates an axial flow, asfurther described below.

Other implementations, for cross flow operations, for instance, do notemploy a wrap or simply use a highly porous cover, e.g., for protecting(from impact, dirt, etc.) the fiber arrangement. Examples of highlyporous covers that can be employed include perforated sheets made ofplastics, metals, and/or fiber glasses, woven or non-woven porousmaterials made of plastics, metals, and/or fiber glasses and so forth.

Ends 28 and 30 of the center tube (also referred to as “extensionpieces” 28 and 30) reach outwardly, beyond the epoxy tubesheets 20 and22. One or both ends 28 and 30 can be constructed into a “nozzle” bymachining one or more o-ring groove(s) into the circumference of theextension piece. When inserted into a corresponding receptacle, o-ringssitting in these grooves ensure the formation of a tight seal for thefluid flows. Other means can be employed for connecting, e.g., inleak-tight fashion, the center tube to conduits for directing a fluidstream into or out of the cartridge.

Ends 28 and 30 can be configured in various ways, presenting a highdegree of flexibility in meeting the demands of any number ofapplications. For example, if only one cartridge is employed in thepurification process, or for systems that include multiple cartridgesinstalled in parallel, one of the ends 28 and 30 can be blocked off by asolid cap or can be inserted into a receptacle that is not communicatingwith any other conduit. On the other hand, systems that includecartridges connected in series can rely on both ends for passing a fluidstream from one cartridge to the next.

In the embodiment of FIG. 2 , end 28 (which can be provided with ano-ring groove supporting an o-ring) is inserted into receptacle 36,configured to accept the nozzle at end 28; the nozzle at end 30 supportsan o-ring, essentially as described above, and is shown without acorresponding receptacle. In the embodiment of FIG. 3 , both ends 28 and30 are shown as being inserted into receptacles 36 and 38, configuredfor connecting with the respective nozzles equipped with o-rings.

A receptacle can be open or closed to fluid communication. In the caseof employing a single cartridge or a system in which multiple cartridgesare installed in parallel, one of the ends 28 and 30 can be blocked offby a closed-off receptacle (or a solid cap). Receptacles designed to beopen to fluid flow can be used when connecting cartridges that areinstalled in series.

Shown in FIG. 4 is cartridge 50 which includes center tube 12, providedwith openings 14, disposed near end 30, and fiber arrangement 52, whichis wound, e.g., helically, around the center tube. Winding techniquesthat can be employed are known in the art. See, for example, U.S. Pat.No. 5,837,033, which is incorporated herein in its entirety by thisreference. Fiber arrangement 52 is partially encased by wrap 24 providedwith opening 26, essentially as described above.

While the embodiments of FIGS. 1-4 are configured for axial orlongitudinal flow (with a fluid stream passing through the fiberarrangement along the length of, e.g., parallel to, the center tube 12),cartridge 70 of FIG. 5 is configured for a transverse or cross-flow modeof operation. Cartridge 70 includes adsorbent fibers that are helicallywound to form fiber arrangement 52 around center tube 12. Whereas inFIGS. 1-4 holes 14 are disposed at the end opposite wrap opening 26, incartridge 70, holes 14 are disposed along the length of the center tube;the solid wrap of FIGS. 1-4 is replaced by porous cover 72, which isoptional.

As discussed in relation to FIGS. 1-5 , the cartridge can be designed tooperate in an axial flow or a cross flow mode.

Shown in FIG. 6 is an axial flow pattern 80, in which a fluid stream tobe purified, namely raw fluid stream 82, is fed from the shell (outerside) of the wound fiber adsorbent arrangement (fabric) 52. In moredetail, the raw fluid enters the fiber arrangement through opening 26 ofwrap 24 and travels through the fiber adsorbent fabric along (e.g., in asubstantially parallel direction to) center tube 12, as indicated by thearrows. At least a portion of the contaminant present in the raw fluidstream 82 is removed by the adsorbent fibers resulting in a purifiedfluid stream, namely clean fluid stream 84, that exits the fiberadsorbent arrangement 52, passing through holes 14 (disposed in thisembodiment near end 30) into the hollow space of center tube 12, to exitthe cartridge at end 30 from the bore side of the center tube. The flowdirection can be reversed (with raw fluid stream being fed from the boreside of the center tube and purified stream exiting the fiberarrangement 52 via wrap opening 26) without an adverse &Tea on theadsorption.

A cross flow pattern also can be employed in some cases. Shown in FIG. 7is cross flow pattern 90 in which a raw fluid stream 82 is fed from theshell side of the fiber adsorbent arrangement (fabric) 52 (which in thisembodiment is not covered or covered by a permeable covering), in adirection that is not parallel to the center tube but at an angle,typically substantially perpendicular, to center tube 12, e.g., asindicated by the arrows. As the raw fluid stream passes through theadsorbent fibers, at least a portion of the contaminant present in thestream becomes captured (adsorbed). A resulting purified stream, namelyclean stream 84, exits the fiber arrangement through perforations 14(which in this embodiment are disposed along the length of center tube12), and leaves the cartridge from the bore side of the center tube. Theflow direction can be reversed (by directing the raw fluid stream fromthe bore side of the center tube, through perforations 14, through fiberarrangement 52 and withdrawing a clean fluid stream from the shell sideof the cartridge) without an adverse effect on the adsorption.

For many practical applications it is useful to assemble adsorbentdevices such as those described with reference to FIGS. 1-5 , forexample, in a system (module). The module employs a vessel having aninlet for introducing a contaminated (raw) fluid and an outlet forcollecting a purified (clean) fluid. The vessel can be made of anysuitable material. Examples include aluminum, plastics, steel, stainlesssteel, fiber glasses, etc., depending on the intended applications.Vessel characteristics such as shape, dimensions, etc. can vary,depending on operation requirements, number of cartridges, cartridgedimensions, mode of assembling and/or operating them, the onsite spaceavailable for installing the module, fluid pressure, temperature, volumeand so forth.

Shown in FIG. 8 , for example, is module 11 in which vessel 13 enclosesa single adsorbent cartridge, in this case adsorbent device 50 (of FIG.4 ). Other adsorbent devices can be employed. Vessel 13 is provided withport 15, an inlet for feeding the fluid stream to be purified, and withreceptacles 36 and 38 (described with reference to FIG. 3 ) andconfigured to receive, respectively, the nozzle at end 28 and at end 30of a center tube.

In module 11, only one receptacle is configured for fluid communication.For example, receptacle 36 can provide a connecting port, specificallyto an outlet for withdrawing a purified fluid from the vessel, whilereceptacle 38 lacks connection to an external port. In a differentapproach, end 30 is blocked, using a solid cap, for instance.

Optionally, one or more centering supports 25 (further described below)can be used to brace ends 28 and/or 30 during installation, to ensure,for instance, that the nozzle at the end of a cartridge properly engageswith the corresponding receptacle.

Although a module containing a single adsorbent device can remove atleast some contaminant is a fluid stream, such a module may not meet thedemands of certain operations. For example, handling large volumes ofraw fluid with a single adsorbent device in a module such as shown inFIG. 8 may turn out to be impractical or prohibitively expensive. Thus,many embodiments of the invention feature modules that include multiple(at least two) adsorbent devices, e.g., within a range of from about 5to about 100 or more, such as within a range of from about 5 to about25, from about 5 to about 50, from about 5 to about 75; or from about 25to about 50, for about 25 to about 75, from about 25 to about 100; orfrom about 50 to about 75, from about 50 to about 100; or from about 75to about 100 cartridges. Illustrative adsorbent modules can contain 3,5, 8, 10, 20, 30, 50, 75, 100 or more adsorbent cartridges.

Vessels enclosing more than one cartridge can have any number of shapesor dimensions. Moreover, within a vessel, cartridges can be arranged invarious configurations. Thus, designing a module may depend on thefootprint available for the purification operation, flow volumes beinghandled, typical pressures encountered in a specific application, and/orother factors.

Some of the module designs can include vessel headers or manifolds forintroducing and/or extracting fluids, for example. Others can useconnecting elements (e.g., tubes, pipes, manifolds or other arrangementsfor directing fluids), supports (e.g., for bracing conduits orcartridges during installation or operation), spacers, and/or othercomponents selected to provide improved mechanical stability, spaceoptimization, synergies among module components, or other purposes.

As an illustration, arrangement 21 of FIG. 9 includes tube coupling 23connecting receptacle 36 (from a first device such as device 50 in FIG.4 ) and receptacle 38 (from a second device such as another device 50 inFIG. 4 ). Tube coupling 23 can be made of steel, plastics, aluminum,fiber glasses, etc. and is dimensioned to accommodate a givenarrangement of adsorbent devices.

Tube coupling 23 can be secured (inside the vessel) using at least onecentering support 25, as illustrated in FIG. 10 . An optional element,centering support 25 can be made of plastics, steel, aluminum, fiberglasses, etc. and can be dimensioned according to he interior vesselgeometry.

As already noted, adsorbent devices within the module can be arranged invarious configurations.

FIG. 11 , for instance, shows module 41 in which vessel 43 houses fiveadsorbent cartridges, such as, for example, adsorbent devices 50 (FIG. 1). The devices are arranged in series and are labeled A through E.Vessel 43 can be a long tube made of steel, aluminum, fiber glasses,plastics or another suitable material and sized to accommodate thenumber and dimensions of the cartridges enclosed. In an illustrativeexample, the tube has a diameter within a range of from about 6 to about30 inches, and a length within a range of 10 to 30 feet.

Port 15 can be connected to exterior piping and can be used for feedingthe raw fluid stream into the vessel. Module ends 47 and 49 includereceptacles that can engage, respectively, with the nozzles of the firstand last adsorbent cartridge. In the embodiment of FIG. 11 , there is nofluid communication at the receptacle at module end 47. Purified fluidis extracted at module end 49, where the receptacle is configured forfluid communication with external piping.

The cartridges are connected to one another using connecting elementssuch as described, for instance, with reference to FIG. 9 . Optionally,the coupling tubes can be supported by centering supports, such asdescribed with reference to FIG. 10 . In more detail, cartridge end 30Ais secured by optional centering support 25. Cartridge A is connected tocartridge B through tube coupling 23AB, optionally supported by one ormore supports 25; cartridge B is connected to cartridge C via tubecoupling 23BC, optionally secured by at least one centering support 25;and so on. In some cases, cartridge end 28E also can be supported by acentering support 25. Centering supports can be positioned at differentlocations within the module. Fewer, more or no centering supports can beemployed.

Some situations render long tube configurations impractical, however.Thus, other adsorbent cartridge arrangements can be used to meet spacelimitations. Shown in FIG. 12 , for example, is cartridge assembly 61including multiple cartridges (e.g., cartridges 50 of FIG. 4 ) arrangedto fit a vessel having a round cross-section.

For some large or extremely large flow applications (such as, forinstance, the direct air CO₂ capture or flue gas CO₂ capture) thecartridges can be arranged in rows, to fit in a vessel or container witha rectangular (e.g., square) cross section. An example is presented inFIG. 13 , showing cartridge assembly 81, which includes rows ofadsorbent cartridges (e.g., cartridges 50 of FIG. 4 ).

Assemblies 61 and 81 illustrate adsorbent devices that are installed ina parallel configuration. Such configurations can be particularly wellsuited for situations in which the height or length of the availablespace is limited. Moreover, assemblies 61 or 81 can be fitted withcommon headers, manifolds and/or other piping arrangements for bringingin raw fluid to be distributed to each adsorbent cartridge. Clean fluidcan be withdrawn from each cartridge and combined into a common outputusing manifolds, reservoirs and/or other suitable piping arrangements.

Cartridges and modules described herein can present additional options.Some relate to operations conducted to regenerate the adsorbent fibersthat contain contaminant removed from the raw fluid.

Releasing the adsorbed contaminant, CO₂, for instance, can be performedusing heat, vacuum, reduced pressure, or any combination thereof. If theregeneration technique relies on heat, the desorption process can be atemperature swing adsorption (TSA) method, while many processes based onlowered pressures are known as pressure swing adsorptions (PSA). Anotheruseful technique that can be employed to release adsorbed species, e.g.,from the porous solid amine adsorbents further described below involvesboth heating and vacuum, the process being known as temperature-vacuumswing adsorption or TVSA. These techniques are well known in the art(see, e.g., U.S. Pat. Nos. 9,457,340, and 8,974,577, the entire contentsof both being incorporated herein by this reference).

If TSA or TVSA techniques are employed, a module such as described inthe present application can be provided with one or more heatingelement(s) that can be used to raise the temperature of the adsorbentfibers, thereby releasing the trapped contaminant and regenerating thefibers. Example of heating elements include but are not limited toheating tapes, heating coils, heating jackets, heat exchanging pipes,heat exchanging plates and so forth.

In some cases, the heating element is external to the vessel containingthe adsorbent cartridge(s). Shown in FIG. 14 , for example, is module101 in which vessel 13, which encloses cartridge 50, essentially asdescribed above, is fitted with heating/cooling jacket 103. The jacketis provided with ports 105 for introducing or withdrawing theheating/cooling fluid utilized in jacket 103. In module 121 of FIG. 15 ,tubular vessel 43, essentially as described with reference to FIG. 11 ,is provided with heating/cooling jacket 123, which has inlet/outletports 105 for the heating/cooling fluid being utilized. Other means ofheating the exterior surface of the vessel can be employed.

One or more heating elements also can be installed in the interior of(within) the vessel containing the cartridges. For example, a heatingjacket, heating coils, heating plates, heating tape, etc. can beinstalled at an interior surface the vessel. To speed up theheating/cooling operation, one or more heating elements can be installedin between, around, among, etc. cartridges present within the module. Insome cases, a cartridge may be individually wrapped or contacted by aheating element. In others, some or all cartridges present can share aheating element.

Shown in FIG. 16 , for instance, is cartridge assembly 141 in whichsingle heat exchanger 143 is located among cartridges arranged in anassembly similar to that described with reference to FIG. 12 . FIG. 17illustrates a section of a cartridge assembly that is similar to that ofFIG. 13 , e.g., is formed of parallel cartridges arranged in rows.Cartridges are heated or cooled by more than one heat exchanger (twoheat exchangers 143A and 143B being shown in the figure). The moduledescribed herein can employ finned tube heat exchangers withlongitudinal or transverse fins, or other suitable types of heatexchangers, as known in the art.

Heat exchanger fluid can enter or exit the heat exchanger via ports 145(FIG. 16 ) or ports 145A and 145B in FIG. 17 ). A header, manifoldand/or other piping (separate from the means for introducing orcollecting fluid being purified in the module) can be dedicated tosupplying or extracting the heat exchanger fluid.

In some embodiments, steam (which is widely available and can representan inexpensive source of heat) is directed into the module to recoverthe adsorbed contaminant, CO₂, for instance.

Temperatures, pressures and/or other parameters relevant to theadsorption or desorption stage can be monitored or controlled usingtechniques and devices known in the art. Adjustments can be made by anoperator, for example. In automated processes, conditions and parameterscan be computer controlled.

The module embodiments described herein offer wide operationalflexibility. Raw fluid, for example, can be ted at the shell or at thebore side of the cartridges. The fluid flow in the module can beconfigured for an axial or cross flow pattern. Series or parallelassemblies can address specific needs.

As one example, FIG. 18 illustrates axial flow configuration 161, withraw fluid 163 being fed from the shell side of cartridges A through E,connected in series as described with reference to FIG. 11 . In moredetail, raw fluid enters vessel 43 at inlet 15, near module end 47, andbecomes distributed, preferably distributed evenly, among cartridges Athough E (as indicated by arrows a, b, c, d, and e). From the shell sideof each cartridge, the raw fluid enters each adsorbent fabric throughwrap opening 26 (FIG. 4 ) and passes through the fabric along (e.g., inparallel to) each center tube (as indicated by the dotted line arrows).Purified fluid leaves each fabric adsorbent and enters the lumen of eachcartridge via holes 14 (FIG. 4 ). With the cartridges connected to oneanother as described with reference to FIG. 11 , purified fluids in thelumen of individual cartridges become combined and exit vessel 43 as acommon purified stream 165 at module end 49.

If desired, a reversed configuration with bore side feeding and shellside collection can be implemented as well, without a negative on theadsorption. It is also possible to operate a module with cartridgeslinked in series in cross flow mode. For example, cartridges 50 in FIG.18 can be replaced with cartridges 70, as described with reference toFIGS. 5 and 7 .

Shown in FIG. 19 is module 201 in which multiple adsorbent cartridges 50(designed for axial flow, as already described) are arranged in parallelin vessel 203, which has a round transverse cross section. Inillustrative examples, vessel 203 has an inner diameter (ID) within arange of from about 30 inches to about 1000 inches. Centrally installedrelative to cartridges 50 is heat exchanger 143, essentially asdescribed above. Heat exchanger fluid is supplied through inlet conduit205 and leaves the vessel via outlet conduit 207. In someimplementations, the heat exchanger is absent, as are the connectionsand ports for the heat exchange fluid.

During operation, the raw fluid enters vessel 203 through inlet port 15and is distributed to the shell side of cartridges 50 through wrapopening 26. With end 28 of each cartridge being closed, e.g., using cap209, the fluid travels through the adsorbent fabric along (e.g.,parallel to) the center tube. At least a portion of the contaminantbecomes trapped by the adsorbent fibers and a purified (clean) fluidpasses from the adsorbent fabric into the interior of each center tubevia holes 14 (FIGS. 4 and 6 ). Individual clean streams exit eachcartridge at ends 30, pass into receiving component 213, which can be apiping arrangement, a manifold, a reservoir, etc., to be combined into acommon purified output which leaves the module via outlet conduit 215.In another approach, individual clean streams exit the vessel throughindividual ports and can be combined as desired outside the vessel.

Module 201 can be operated in a reverse manner, with bore side feedingand shell side collection without an adverse effect on the adsorption.

In FIG. 20 , module 301 includes rows of cartridges 50 (see FIG. 13 ,for instance) enclosed in vessel 303 which has a rectangular, e.g.,square, cross section. Vessel 303 can have a length within a range offrom about 5 to about 50 feet and a height within a range of from 40 to100 inches. Rows of cartridges can be accommodated using other vesselshapes and/or dimensions.

A group of adsorbent devices 50 is heated by heat exchangers 43. Heatexchanger fluid enters the module via inlet conduit 305, is distributedto heat exchangers 43 via header 307 and exits vessel 303 via outletconduit 309.

Raw fluid is introduced to vessel 303 via inlet conduit 15 and enterseach cartridge 50, from the shell side, via wrap opening 26. With end 28capped (using cap 209, for example), raw fluid proceeds through theadsorbent fabrics along the center tubes, in an axial flow patternessentially as described above. Clean fluid exits the fabrics, passes tothe lumen of the center tubes via holes 14 (FIGS. 4 and 6 ) and exitseach cartridge at end 30. Individual clean streams can be collected andcombined using manifold 313 or another suitable collection arrangement.A common clean output stream leaves vessel 303 through outlet conduit315.

In a different approach, individual output streams from ends 30 ofcartridges 50 exit the module through individual ports and can becombined outside the vessel. A reversed input-output configuration, withraw fluid being fed from the bore side of each individual cartridge, andpurified fluid being collected at the shell side of the cartridges canbe implemented without a detrimental effect on the adsorption.

For cross flow operation, cartridges 50 in module 201 or 301 can bereplaced with cartridges designed for cross flow, as described withreference to FIGS. 5 and 7 , for example. In this approach, the rawfluid stream can be fed from the shell side of the fiber adsorbentcartridges and travels through the adsorbent fabric in a directionsubstantially perpendicular to the center tube. From the adsorbentfabric, purified fluid passes into the lumen of the center tubes 12(through holes 14 disposed, e.g., as shown in FIG. 5 ) and exits eachcartridge from the bore side of the center tube. Individual purifiedstreams obtained from individual cartridges can be combined in a commonpurified output within or externally to the vessel. The flow directioncan be reversed (with raw fluid being fed from the bore side and cleanfluid withdrawn from the shell side) without an adverse effect on theadsorption process.

More than one module can be employed, to meet the requirements of aspecific application, for instance.

In contrast to modular arrangements that employ hollow fiber membranes,contaminants such as acid gases are trapped or captured in the adsorbentmaterial, which can be regenerated by cycling processes. Thus, themodule designs described herein do not need to provide for theextraction of a fluid fraction that is enriched with contaminant, as inthe case of membrane separation systems.

The adsorbent fibers employed in the modules described herein can beformed using any suitable adsorbent material. Examples include zeolites,MOFs, COFs, PAFs active carbon and others. In some cases, the adsorbingmaterial is dispersed in a porous polymer matrix, as described, forinstance, in U.S. Pat. Nos. 10,525,399 and 10,525,400; and U.S. PatentApplication Publication Nos. 20210008523 and 20210031168. The contentsof these documents are incorporated herein by reference in theirentirety.

In an illustrative implementation, the adsorption device and/or themodule include(s) a porous solid amine adsorbent that is particularlywell suited for the removal of an acid gas from contaminated fluidstreams. Such an adsorbent is described in U.S. Provisional ApplicationNos. 63/220,734 and 63/220,745, both filed on Jul. 12, 2021, in U.S.Non-Provisional Patent Application filed concurrently herewith, underAttorney Docket No. 0413.0004US1, and the International PatentApplication, filed concurrently herewith under Attorney Docket No.0413.0004WO1, the entire contents of these documents being incorporatedherein by this reference. As seen in these documents, porous solid amineadsorbents, typically robust and self-supporting, can be prepared bycontacting a first solution with a second solution.

Among the constituents of the first solution is an amine-containingcompound (a substance that includes functional groups such as —NH₂,—RNH, or —RR′N), and another polymer.

In specific embodiment, the amine-containing compound is a water-solubleamine-containing polymer. As used herein, the term “amine-containingpolymer” or “amine polymer” refers to polymers that contain —NH₂, —RNH,or —RR′N functional groups attached to/separated by —CH₂CH₂—,—CH₂CH₂CH₂—, or —CH₂CH₂CH₂CH₂—. The R and R′ groups can be methyl,ethyl, propyl, etc. groups and can be the same or different.

The water-soluble amine polymer can be provided in a wide range ofmolecular weights, from about 400 to about 10,000,000, for example. Someimplementations utilize a water-soluble amine polymer within a range offrom about 1,000 to about 1,000,000.

In one example, the water-soluble amine compound (e.g., polymer)includes a unit skeletal structure represented by Formula 1:

—[(CH₂)_(x)—NR]_(y)—  (1)

In the unit skeletal structure, R may be hydrogen or a branched chain; xis an integer of 1 to 4, and y is an integer of 2 to 1,000,000. Inspecific implementations, the amine compound is a linear or branchedpolyethylenimine (for x=2) or a linear or branched polypropylenimine(for x=3).

In another example, the water-soluble amine compound (e.g., polymer)includes a structure represented by Formula 2:

—[(CH₂)_(x)—CH(NH₂)]_(y)—  (2)

where x is an integer of 1 to 4 and y is an integer of 2 to 1,000,000.In specific implementations, the amine compound represented by Formula 2is a polyvinylamine (in the case of x=1).

The amount of the water-soluble amine compound can be within a range offrom about 5 to about 50% based on the total weight of the first (e.g.,dope) solution.

The first solution also includes another constituent, typically a waterinsoluble polymer. The water insoluble polymer forms a porous polymericstructure upon contact with a solvent such as water, providing amechanical support for the porous solid amines formed from the reactionwith a multifunctional acid. In the absence of a water insolublepolymer, the porous solid amine adsorbent will be sticky and difficultto shape into a desired configuration.

Water insoluble polymers that can be utilized to prepare the firstsolution can be natural or synthetic. Examples of natural polymersinclude lignin, cellulose, cellulose derivatives, (such as celluloseacetates, for instance), and others. Examples of synthetic polymersinclude polyacrylonitrile, poly(methyl methacrylate), polystyrene,polyethylene terephthalate), aromatic polyamides, aliphatic polyamides,polyesters, polyetherketones, polyethersulfones, polyetheresters,polysulfones, polyvinyl fluoride, polybenzimidazoles, polybenzoxazoles,polyazoaraomatics, poly(2,6-dimethylphenylene oxide), polyphenyleneoxides, polyureas, polyurethanes, polyhydrazides, polyazomethines,polyacetals, polyquinoxaline, polyamideesters, polyacetylenes, polymerwith intrinsic porosities (PIMs), polyesters, any combinations (blends)or copolymers thereof.

Many embodiments of the invention utilize water insoluble polymers thatexhibit a glass transition temperature or a melting point above 100° C.Advantageously, such polymers are expected to withstand temperaturesemployed during the thermal regeneration of the adsorbent, without asignificant pore collapse.

The amount of water-insoluble polymer in the first solution can bewithin a range of from about 5 to about 50 weight %.

The first solution can be prepared by combining the water insolublepolymer and the water-soluble amine polymer in a polar solvent. In manyimplementations, the polar solvent is an organic liquid that is misciblewith water. It can dissolve the amine polymer as well as thewater-insoluble polymer. Examples include but are not limited toethanol, propanol, n-butanol, tetrahydrofuran (THF), dimethylformamide(DMF), dimethylacetamide (DMAc or DMA), dimethylsulfoxide (DMSO),N-methyl pyrrolidone (NMP), or mixtures thereof. Other polar solventscan be employed.

The polar solvent can be present in the first solution in an amountwithin a range of from about 50 to about 90 wt %.

The first solution can be a homogeneous solution in which all threecomponents, namely the water-insoluble polymer, the water-soluble aminepolymer and the polar solvent, are miscible.

The first solution can include other ingredients such as, for instance,a non-solvent component and/or a particulate material.

In one typical implementation, the second solution is an aqueoussolution containing a multivalent (multifunctional) acid, i.e., an acidhaving two or more acid functional groups. In another typicalimplementation, the second solution is an aqueous solution containing amultivalent metal ion, such as Ca²⁺, Cu²⁺, Zn²⁺, and Me²⁺.

The aqueous solution can include water in an amount of at least 80%based on the total weight of the aqueous solution, preferably in anamount that is equal or greater than 95 wt %.

The multifunctional acid can be an inorganic acid, such as sulfuric acidor phosphoric acid, or an organic acid. Examples of suitablemultifunctional organic acids (having two or more —COOH groups) includeoxalic acid, citric acid, malic acid, tartaric acid, humic acid,dithiodipropionic acid, succinic acid, sulfosuccinic acid, phytic acid,trans aconitic acid, polyacrylic acid and its copolymers,polyvinylphosphonic acid and its copolymers, polystyrene sulfonic acidand its copolymers, polystyrene phosphonic acid and its copolymers,polystyrene carboxylic acid and its copolymers, and the like, or anymixtures thereof.

In one example, the acid concentration in the aqueous solution is in therange of 0.01% to 30%, preferably in the range of 0.1% to 10% relativeto the total weight of the aqueous solution.

In some cases, the second solution is simply an acid-water solution. Inothers, the second solution further includes one or more additive(s).

Porous solid amine adsorbents are prepared by bringing together the twosolutions. In many cases the product is formed rapidly, e.g., in amatter of seconds.

Porous solid amine adsorbents also can be prepared by contacting a first(dope) solution such as described above with a second solution thatcontains a metal ion (Cu²⁺, for instance) that can form a multiligandmetal complex. The metal ion can be a component in a multifunctionalmetal salt. Procedures are described in U.S. Provisional Application No.63/220,745, filed on Jul. 12, 2021, U.S. Non-Provisional PatentApplication filed concurrently herewith, under Attorney Docket No.0413.0004US1, and International Patent Application, filed concurrentlyherewith under Attorney Docket No. 0413.0004WO1, the entire contents ofthese documents being incorporated herein by this reference.

Without wishing to be bound by any particular theory or interpretation,it is believed that once the first solution (e.g., dope) is brought intocontact with the aqueous solution containing a multifunctional chemicalagent (e.g., a multifunctional acid or metal salt), the water insolublepolymer chain is frozen into solid state by a non-solvent induced phaseinversion, while the water soluble amine compound is frozen into solidstate by a rapid crosslinking reaction between at least some of theamine functional groups and the multifunctional chemical agent. It isfurther believed that without the multifunctional chemical agent, thewater-soluble amine compound would become rapidly diffused into thewater solvent precluding the formation of a functional adsorbent.

The porous solid amine adsorbent can be fabricated in various formsincluding fibers, hollow fibers and others. To form a (non-hollow)porous solid fiber, for example, the first (dope) solution (containing awater insoluble polymer and a water soluble amine polymer) can beextruded through a needle, passed through air, then brought into contactwith the second solution (namely the aqueous solution containing amultifunctional acid). Techniques that can be followed or adapted aredescribed, for example, in U.S. Pat. No. 5,181,940, except that no borefluid is utilized.

In illustrative examples, the porous solid amine adsorbents arefabricated in fibers (which can be hollow or non-hollow fibers) havingany desired outer diameters, e.g., within a range of from about 5 mil toabout 50 mil. Other properties characterizing the fibers prepared asdescribed herein (such as, for instance, a surface porosity that can bein the range of 1% to 60% by area) can be obtained by selecting oradjusting the equipment design, the process conditions or other factors.

The porous solid amine adsorbents, e.g., in the shape of fibers, can befurther processed. In an optional step, for example, the porous solidamine adsorbents can be washed with water, alcohol or another suitablewashing medium, e.g., to remove the solvent as completely as possible.

The porous solid adsorbent obtained by contacting the first and secondsolution, optionally washed, can be dried under ambient conditions or inan oven, e.g., at temperatures such as from 50° C. to 100° C. In somecases, heat treatment (in a suitable oven, for instance) can beundertaken, e.g., to impart desired mechanical properties to the productadsorbent.

In some embodiments, the adsorption device or the module is employed toremove an acid gas contaminant (CO₂, H₂S, SO₂, for instance) from afluid stream such as flue gases, biogas, hydrogen gas, natural gas orair. The acid gas released from the adsorbent fibers can be stored orused in other applications. For example, the carbon dioxide desorbedfrom the fibers employed in the cartridge can be utilized for enhancedoil recovery, to prepare synthetic fuels, such as methanol, methane, jetfuels, etc. In some embodiments, the carbon dioxide is injected forstorage.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

What is claimed is:
 1. A fluid purification system, the systemcomprising: a vessel provided with an inlet for introducing a fluid tobe purified and an outlet for collecting purified fluid; at least oneadsorbent device within the vessel, the at least one adsorbent devicecomprising multiple adsorbent fibers; and an optional heating element atthe exterior or in the interior of the vessel.
 2. The fluid purificationsystem of claim 1, wherein the adsorbent fibers are disposed along alength of or wound around a hollow center tube, forming a fiberarrangement, fluid communication between a shell side of the fiberarrangement and an interior space of the center tube being through oneor more openings defined in the hollow center tube.
 3. The fluidpurification system of claim 1, further comprising one or morereceptacles for engaging the at least one adsorbent device.
 4. The fluidpurification system of claim 1, wherein the vessel includes multipleadsorbent devices connected in series.
 5. The fluid purification systemof claim 1, wherein the vessel includes multiple adsorbent devicesarranged in a parallel configuration.
 6. The fluid purification systemof claim 1, wherein the optional heating element is a heating jacket ora heat exchanger.
 7. The fluid purification system of claim 1, whereinthe fluid purification system is configured for axial flow or whereinthe fluid purification system is configured for cross flow.
 8. The fluidpurification system of claim 1, wherein the fluid purification system isconfigured for shell side feeding, or wherein the fluid purificationsystem is configured for bore side feeding.
 9. The fluid purificationsystem of claim 1, wherein the multiple adsorbent fibers form a fiberarrangement having an exterior surface.
 10. The fluid purificationsystem of claim 9, wherein the exterior surface of the fiber arrangementis partially wrapped by an impermeable stainless steel sheet, a coppersheet or a fiberglass sheet.
 11. The fluid purification system of claim9, wherein the exterior surface of the fiber arrangement is not coveredor covered by a perforated plastic material.
 12. The fluid purificationsystem of claim 1, wherein the adsorbent fibers include a zeolite,activated carbon, MOF, COF or PAF material, or wherein the adsorbentfibers include linear polyethylenimine, branched polyethylenimine andpolyvinylamine, or wherein the adsorbent fibers include a crosslinkedlinear polyethylenimine, crosslinked branched polyethylenimine andcrosslinked polyvinylamine, or wherein the adsorbent fibers include aporous solid amine adsorbent in which an amine-containing polymer isembedded in a polymeric matrix.
 13. A process for removing a contaminantfrom a fluid stream containing the contaminant, the process comprising:directing the fluid stream to a module containing at least one adsorbentdevice, wherein the adsorbent device includes adsorbent fibers; bringingthe fluid stream in contact with the adsorbent fibers, whereby at leasta portion of the contaminant is adsorbed by the adsorbent fibers toproduce a purified fluid stream; and collecting the purified fluidstream from the module.
 14. The process of claim 13, further comprisingregenerating the adsorbent fibers.
 15. The process of claim 13, furthercomprising desorbing the at least a portion of the contaminant from theadsorbent fibers by heat, reduced pressure, vacuum, or a combination ofheat and reduced pressure or vacuum, thereby regenerating the adsorbentfibers.
 16. The process of claim 13, wherein the adsorbent fibers aredisposed along a length of or wound around a hollow center tube, formingan adsorbent arrangement, fluid communication between a shell side ofthe adsorbent arrangement and an interior space of the hollow centertube being through one or more openings defined in the center tube. 17.The process of claim 13, wherein the module includes multiple adsorbentdevices arranged in series or wherein the module includes multipleadsorbent devices arranged in a parallel configuration.
 18. The processof claim 13, wherein the process is configured for axial flow or whereinthe process is configured for cross flow.
 19. The process of claim 13,wherein the process is configured for shell side feeding or wherein theprocess is configured for bore side feeding.
 20. The process of claim13, wherein the fluid stream containing the contaminant is a flue gas, abiogas, hydrogen gas, natural gas or air, or wherein the contaminant iscarbon dioxide, hydrogen sulfide or sulfur oxide.
 21. The process ofclaim 13, wherein the adsorbent fibers include a material selected fromthe group consisting of zeolites, activated carbons MOFs, COFs and PAFs,or wherein the adsorbent fibers include linear polyethylenimine,branched polyethylenimine and polyvinylamine, or wherein the adsorbentfibers include a crosslinked linear polyethylenimine, crosslinkedbranched polyethylenimine and crosslinked polyvinylamine, or wherein theadsorbent fibers include a porous solid amine adsorbent in which anamine-containing polymer is embedded in a polymeric matrix.
 22. A fluidpurification device, the device comprising: a plurality of adsorbentfibers disposed along a length of a center tube or wound around thecenter tube, wherein: the center tube is hollow; and fluid communicationbetween a shell side of the plurality of adsorbent fibers and aninterior space of the center tube is through one or more openingsdefined in the center tube.